1-amino-2-nitrobenzene-4-sulfonic acid amides



may.

United States Patent l-AMINO-Z-NITROBENZENE- t-SULFONIC ACID AMIDES Ernst Merian, Allschwil, Switzerland, assignor to Sandoz Ltd., Basel, Switzerland No Drawing. Filed Oct. 24, 1958, Ser. No. 769,283

Claims priority, application Switzerland Feb. 22, 1954 8 Claims. (Cl; Mill-397.7)

Only a few disperse dyestuffs are known which dye acetate rayon in yellow shades having sutficient fastness to withstand washing at elevated temperatures Without undergoing change of shade or bleeding on adjacent material. The afiinity of these dyenstuffs for acetate rayon, however, is insuflicient.

The present invention relates to disperse dyestuffs which have good affinity for acetate rayon; They dye this fiber in yellow shades of very good fastness to washing and excellent fastness to light and to gas fumes. The dyestuffs are water-insoluble derivatives of 1-amino-2-nitro-- benzene-4-sulfonic acid amide and correspond to the formula a wherein R stands for a mononuclear radical of the benzene series,

R stands for a radical of the aliphatic, cycloaliphatic or araliphatic series which may be further substituted or for a radical of the benzene. or naphthalene series,

R stands for hydrogen or a radical of the aliphatic series which may be further substituted, or. standstogether with N and R -for the radical of a saturated heterocyclic amine,

R stands for a radical of the aliphatic, cycloaliphatic or araliphatic series which is difierent from R and may be further substituted, or a radical of the benzene series carrying at least one aliphatic ether groupadjacent to the benzene nucleus or linked to it by an oxygen atom and which may contain hydroxyl groups,

or standswhen R representsa radical of thecycloaliphatic, araliphatic or aromatic series-also for a radical of the benzene series containing at least one hydroxyalkyl group adjacent to the benzene nucleus. or linked to it by an oxygen atom,

R stands for hydrogen or a radical of the aliphatic series which may be further substituted, and wherein at least one of the symbols R and R represents or contains a cyclic radical, and

.2: stands for chlorine or bromine, and

l p N 2,977,376

Patented Mar. 28,1961

R and R have the previously-recited significances.

Valuable dyestuffs are also obtained when mol of a 1-halogen-Z-nitrobenzene 4-sulfonic acidamidezof the Formula I is reacted with 1 mol of amixture in:

any desired proportions of two or more difierent amines: of the Formula II, or

1 mol of a mixture in any desired, proportions of. two or: more diiierent 1--halogen-2-nitrobenzene-4 sulfonic acid; amides of the Formula I with 1 mol'of an amine of the; Formula II, or

1 mol of a mixture in any desired proportions of two or-- more different 1-halogen-2-nitrobenzene-4-sulfonic acid amides of the Formula I with 1 mol of a mixture in any desired proportions of two or more different. amines of the Formula II.

Finally it is possible to replace the mixtures of two ormore different amines of the FormulaII by mixtures in any desired proportions of one or more amines of the Formula II plus a monoor bi-nuclear cycloaliphatic or: aromatic amine which differs from the amines: of For-- mula II and contains no water-solubilizing groups.

The reaction of the l-halogen-Z nitrobenzene-4-sulfonic acid amides of the, Formula I with the amines of the Formula II or mixtures of aminesis best conducted at elevated temperature. Water is an excellent reaction? medium; a Wetting agent may be added, or alternatively an organic solvent, e.g. ethanol, benzyl alcohol, benzene, toluene, etc. An addition of a suitable acid-binding agent such as sodium acetate, sodium carbonate or so dium bicarbonate has a favorable influence on condensation in mostcases. excess of the appropriate amine or amines.

The 1-ha1ogen-2-nitrobenzeneA-sulfonic acid amidesi used as starting materials for performing this invention can, be produced'by the recognized methods, i.e. by treat-- ing 1-halogen-2-nitrobenzene-4-sulfonic acid halideswith aliphatic, cycloaliphatic, .araliphatic, heterocyclic and aroa. matic amines under mild conditions. The resulting amides, some of which are new, can be characterized byv their melting points: i I

Melting 1-chloro-2-11itlobenzeneiesulfonic acidp nis t,

-]I1ethylqmirln 63 -el;hylamirin i 94;- -isopropylamide 79 -n-hexylamide 73 -(2-ethyl)-hexylamirlp 383: H -(2-hydroxy)-ethyla 126 -(3'-methoxy)-propyl mi 631. -henz vlamidc a 105,. -cyclohexylamide 86 -phenylan1ida -(2-met.hyl)-phcny1amide 145,, -(3-methyl)-phenylarnide 84 -(4-methyl)phenylamirle 126:. -(4-methoxv)-phenylarnide 156] -{4-[2-(2"-methoxy) y] 98,. -(2',5-dichloro)-phenylamide. 155 I -naphthyl(l)-amide i 169 -(5,6,7,8-tetrahydro)-naphthy1(1)-amide 1 643 morpholide 156, -dimethylamide 106:- -di-(2-hydr0xyethyl)-amide -N-phenyl-N-(2-hyrlroxy)-ethylamide 106 -N-(2-methyl)-phenyl-N-(2'-hydroxy)-eth am 119: -N-(3-methyll-phenyl-N"(2'-hydroxy)-ethylamide. 1,00 -(2-hydroxy)-propylamide m 102 -di-(2'-hydroxypropyl)-amide 162'; -N-methyl-N-(2-hydroxy)-ethylamide g The same efiect is achieved with'an- This table merely illustrates the type of the l-halogen- Z-nitrobenzene-4-sulfonic acid amides which may be used, and is not intended to be exhaustive.

As examples of amines of the Formula II suitable for carrying out the reaction with 1-halogen-2-nitrobenzene- 4-sulfonic acid amides according to the present invention, the following may be enumerated:

aminomethane,

aminoethane,

aminopropane,

aminoisopropane,

aminobutane,

aminopentane,

aminohexane,

aminooctane,

aminodecane,

l-amino-Z-hydroxyethane,

1-amino-2-hydroxypropane,

1-amino-3-hydroxypropane,

l-amino-2,3-dihydroxypropane,

aminohydroxybutane,

aminohydroxypentane,

l-amino-Z-methoxyethane,

1-amino'2-methoxypropane,

l-amino-3-methoxypropane,

1-amino-2-hydroxy-3-methoxypropane,

1-amino-2-morpholylethane,

1-amino-3-morpholylpropane,

benzylamine,

l-amino-Z-phenylethane,

aminocyclohexane,

amino-methylcyclohexane,

amino-dimethylcyclohexane,

l-amino-l,2,3,4-tetrahydronaphthalene,

Z-amino-l,2,3,4tetrahydronaphthalene,

1-amino-2- or -3- or -4-(2'-methoxy or -ethoxy or -propoxy or -butoxy)-ethoxybenzene,

1-amino-2- or -3- or -4-[2'-(2"-hydroxy)-ethoxy]-ethoxybenzene,

1-amino-2- or -3- or -4-[2'-(2"-methoxy or -ethoxy or -propoxy or -butoxy)-ethoxy]-ethoxybenzene,

1-amino-2- or -3- or -4-[2'- or 3-(2"- or 3"-hydroxy)- propoxyJ-propoxybenzene,

1-amino-2- or -3- or -4-methoxymethylor -ethoxymethylbenzene,

l-amino-Z- or -3- or -4-(2'-methoxy or -ethoxyl)-ethoxymethylbenzene,

1-amino-2- or -3- or -4-[2-(2"-hydroxy)-ethoxy]-ethoxymethylbenzene, Y

1-amino-3-(2'-hydroxy)-ethoxymethyl-4-methylbenzene,

1-amino-3-(2'-methoxy or -ethoxy)-ethoxymethyl-4-methylbenzene,

l-amino 3,5 di-[(2'-hydr0xy)-ethoxymethyl]-4-methyl-.

benzene,

1-amino-3,5-di-[(2'-methoxy or -ethoxy)-ethoxymethyl]- 4-methylbenzene, 2-(3'-amino)-phenyldioxolane, amino-saligenin-methylene ether,

x-aminol- [2- 2-hydroxy) -ethoxy] -ethoxylnaphthalene,

1-amino-2- or -3- or -4hydroxymethylbenzene, 1 -amino-2- or -3- or -4-(2-hydroxy)-ethylbenzene, l-amino-Z- or -3- or -4-(2- or 3'-hydroxy)-propylbenzene,

I-amino-Z- or -3- or -4-(2',3'-dihydroxy)-propylbenzene,

l-amino-Z- or -3- or -4-(2'- or 3'-hydroxy)-propoxybenzene,

I-amino-Z- or -3- or -4-(2.3'-dihydroxy)propoxybenzene,

1-amino-2- or -3- or -4-(4'-hydroxy)-butoxybenzene,

l-amino-3-chl0ro-4- or -6-(2-hydroxy)ethoxybenzene,

1amino-3-chloro-4-(2' or 3-hydroxy)- or -(2'.3' -dihydroxy)-propoxybenzene,

1-amino-3-bromo-4- or -6-(2hydroxy)-ethoxybenzene.

A preferred sub-group of dyestuffs according to the present invention are the 1-amino-2-nitrobenzene-4-sulfonic acid amides which correspond to the formula wherein Y stands for a member selected from the group consisting of phenyl, methylphenyl, naphthyl, tetrahydronaphthyl, cyclohexyl and benzyl, Z stands for a member selected from the group consisting of hydrogen and lower hydroxyalkyl, R stands for a member selected from the group consisting of lower hydroxyalkyl, lower hydroxyalkoxyalkoxy, lower alkoxyalkoxy and, when y is different from phenyl, lower hydroxyalkoxy and lower alkoxyalkoxyalkoxy and, when R; is a substituent containing at least one oxygen atom, also hydrogen and methyl, R, stands for a member selected from the group consisting of hydrogen, chlorine, lower hydroxyalkyl, lower hydroxyalkoxyalkyl, lower alkoxyalkoxyalkyl and lower alkoxyalkoxyalkoxyalkyl.

The following examples illustrate the invention without in any way limiting its scope. The proportions refer to parts by weight; temperatures are in degrees centigrade.

Example 1 36.4 parts of lchloro2-nitrobenzene-4-sulfonic acid phenylamide are heated in 100 parts of ethanol to boiling point. 20 parts of aminocyclohexane are then added dropwise to the solution. After 1 /2 hours the hot mass is filtered to remove small quantities of impurities. Upon cooling, the 1-cyc1ohexylamino-2-nitrobenzene-4-sulfonic acid phenylamide of the formula NO: CHr-CH: H20 /CHNH SOs-NH CHr-CHn crystallizes out from the intensely yellow solution. It melts at 142. When this compound is processed in the usual way to give a dye preparation, e.g. by grinding with a dispersing agent and with sodium sulfate, a powder is obtained which dyes acetate rayon from aqueous dispersion at elevated temperatures in bright greenish yellow shades having outstanding fastness properties. Such dyeings are notable for their exceptionally good fastness to washing. This dyestuff also dyes synthetic polyester fibers of the nylon and polyester fibers of the Dacron type in greenish yellow shades possessing very good fastness properties.

The new dyestufl is distinctly superior to l-cyclohexylamino-Z-nitrobenzene-4-sulfonic acid cyclohexylamide in its affinity for acetate rayon and also to l-cyclohexylamino-2-nitrobenzene-4-sulfonic acid amide in its washing fastness on acetate rayon.

Example 2 16 parts of 1-chloro-2-nitrobenzene-4-sulfonic acid di- (2'-hydroxyethyl)-amide are heated together with 5 parts of aminocyclohexane and 40 parts of water to boiling point. The hydrochloric acid thus liberated is neutral ized by an addition of 4.2 parts of sodium bicarbonate.

' After 2 hours the product is cooled, the mother-liquors The dyestufi solidifies rapidly. It corresponds tothe When crystallized from an ethanol solution, it has a melting point of 115. -It dyes acetate rayon in greenish yelloi'l sha es which are fast to washing.

A similar dyestuff is obtained when l-bromo-Z-nitro- 1 benzene-4-sulfonic acid N-ethyl-N-(2f-hydroxy)-ethylamide is condensed in an analogous manner with aminocyclohexane. Itcorresponds to'the formula nitrobenzene-4-sulfonic acid di-(2-methoxyethyl)-arnide with am-inocyclohexane also dyes acetate rayon is green- NO: H:C- -H:C-0,

HC-HzCOONH-S0:NH HsC-HzC-O/ V ish yellow shades which are fast to washing. It corre- Example, 4

sponds to the formula cat-om orn-om-o-cn, In a similar way the following greenish yellow dispersion dyestuffs may be obtained from the corresponding l-chloro-2-nitrobenzene-4-sulfonic acid amides; l-cyclohexylamino-2-nitrobenzene-4-sulfonic acid N-methyl-N- (2'-hydroxy)-propylamide, l-cyclohexylamino-Z-nitrobenzene-4-sulfonic acid N-methyl-N-(2'-hydroxy)-butylamide, l-cyclohexylaminoJenitrobenzenea l-sulfonic acid N-ethyI-N-(T-hydroxy)-propylamide, 1 -cyclohex-y-lamino Homo-mo- OO NHO-SOr-NHO 50 When converted into a dye preparation in the normal way, the new dyestuff dyes acetate from aqueous disper- 2-nitrobenzene-4-sulfonic acid 'N-e'thyl-N=(2'-hydroxy)- butylamide, l-cyclohexylamino 2 nitrobenzene-4-sulfonic 2-nitrobenzenel-sulfonic acid N-(2'-methoxy -lethylamide, 1-cyclohexylamino:2 nitrobenzenerelesulfonic acid In a similar way the following slightly less reddish dis- I persion dyestuffs may be obtained from l-chloro-Z-nitroi V benzene-4-sulfonic acid phenylamide:

nitrobenzene-4-sulfonic acid N-phenyl-N-(2-methoxy)- ethylamide, l-cyclohexylamino-2-nitrobenzene-4-sulfonic acid N-phenyl-N-(2'-hydroxy)-propylamide and l-cyclohexylamino-2-nitrobenzene 4-sulfonic acid N-phenyl-N (3'-methoxy) -propylamide.

Example 3' 21.5 parts of 1-amino-4-[2'-(2"-methoxy)-ethoxy] ethoxybenzene are stirred into parts of water.

thus obtained is heated to boiling point and stirred ion 2. hours at this temperature. Upon' coolingthe product separates from the mass; it is then filtered and washed,

first with water and then with a little ethanol. 'The' new yellow dyestutf may be crystallized from four times its weight of ethanol, from which it separates in needles. having a melting point of 114. It corresponds to they formula When converted into a dye preparation in the normal manner, it dyes acetate rayon and synthetic polyamide fibers from aqueous dispersionin reddish yellow shades which are fast to light andsubliming. Dyeings on acetate rayon are specially noteworthy for their outstanding fastness to washing. Thus they withstand treatment in an aqueous solution containing 0.5% soap and 0.2% soda 20 for 45 minutes at 71 (Wash Test No. 3, 1953 Technical Manual and Year Book of the American Association of Textile Chemists and Colorists, pages 91-92) without undergoing change of shade or bleeding onto adjacent acetate and viscose rayon.

if h f hl 2 25 A similar dyestufl is obtained by reacting, in analogous The dyestu P c d by t e reaction 0 l-c oromanner, l-chloro-2 nitrobenzenel-sulfonic acid phenylamide with 1-amino-4-(2',2'-diethoxy)-ethoxybenzene. It corresponds to the formula 10.4' parts of 1-chloro-2-nitrozenzene-4-sulfo1tic acid phenylamide and 6 parts of l-amino-4-(2'-h droxy)- The suspension is heated to boiling point, 3 parts of sodium 0 bicarbonate added in portions, and the whole stirred for 4 hours at 90-l00. The dyestuff gradually separates out I U in solid form and after cooling the mass is removed by filtration. After washing and drying, a yellow-brown powder is obtained which can be crystallized to form 4 orange colored needles having a melting point of 140.

It corresponds to the formula -sion in reddish yellow shades which are fast to light and subliming. The dyeings are characterized by very good fastness to washing;

methyl) phenylamino 2 nitrobenzene-c -sulfonic acid phenylamide, 1-[4'-(l-hydroxy)-ethyl]-phenylamino-2- nitrobenzene-4-sulfonic acid phenylamide, l-[3-(l"-hydroxy) -ethyl] -phenylamino-2-nitro benzene-4-sulfonic acid a a phenyl amide, l-(3-hydroxymethyl 4' methyDf-phenyl:

Vamino-2-nitrobenzene-4-sulfonic acid phenylamide, 1-[ 3'- ethoxybenzene, 31.2 parts'of l chloro-2 nitrobenzene-4- (1" hydroxy) ethy1 4' m0thy1] pheny1amino 2 nitrben f I zene-4-sulfonic acid phenylamide, .l-[3'-(2"-methoxy) sulfonic acid phenylamide and 8 .4 parts of'sodium bicarv V t bonate are stirred into ldparts of waters The-emulsion ethoxymethyl '4' methyl]-phenylamino-Z-nitrobenzehe- A Example Melting Shade of Dyeing N0. R1 R: R; R4 Point, on Acetate C. Rayon 1 (5,6,7,8-tetrahydro) -naph- H 4 (2 7 hydroxy) ethoxy 173 reddish yellow.

thyl. phenyl. phenyl Z-hydroxy- ...do 74 Do.

ethyl. V rln H 4-(2-vhydroxy)-ethylpheiiyL. 89 neutral yellow. eyelohexyl H d'0:. 159 Do. phenyl H 4-methyl-3-(2'-hydroxy)- 112 Do.

ethoxymethylphenyl. cyclohexyl H 4-methyl-3'(2-methoxy)- 114 D0.

ethmtymethylphenyl. do H.- 4-methyl-3-l2'-hydrbxy)- 121 Dotethoxyniethylphenyl. do H 4 1i1ethyl-3-[2'-(2-methoxy 91 Do.

ethoxy] ethoxymethylphenyl. phenyl H 3-hydroxymethylphenyl H .1 107 D0. do H ethyl ethyl 106 greenish yellow.

2-hydroxypropyl 2-hydroxy cyclohexyl Ht; 124 Do.

. p py The following are formulae of some of the products of the foregoing examples:

Example 34 NO: GHQ-CH1 CH-NH- CHFC 1 e soz-N-onrcm-cm-o H.

Example 78 Example 79 intimate mixture of- 1 part of the dyestu-if of the formula 1 part of the dyestuif of the formula produced according to the process described in Examples 1 to 4, by condensing 3 mols of aminocyclohexane with a mixture of 1 mol of 1-chloro-2-nitrobenzene-4-sulfonic acid phenylamide, 1 mol of 1-chloro-Z-nitrobenzene-4-sulfonic acid dimethylamide and 1 mol of 1-chloro-2-nitrobenzene-4-sulfonic acid benzylamide, or by making a paste which may be dried of the three dyestuffs, dyes acetate rayon from aqueous dispersion in fast greenish yellow shades.

Mixtures of the above-mentioned type are of especial value. They often dye acetate rayon in stronger shades than the individual dyestuffs do when the same amount of dyestuif is used. These mixtures, therefore, are of higher money value than the individual dyestufis. 1

The mixtures of especial interest are those which contain at least two derivatives of the l-amino-Z-nitrdber'i zene-4-sulfonic acid amide corresponding to the formula on on i BIC /OH-NH SO:-

CHrCH: b

wherein a denotes an aliphatic, cycloaliphatic or araliphatie radical or a radical of the benzene, naphthalene or hydronaphthalene series,

and

b denotes hydrogen or an aliphatic radical.

Example A dyebath is prepared with 0.6 part of the dyestuif obtained according to Example 3 and dispersed with the aid of turkey red oil, 6 parts of a sulfonated fatty alcohol and 3000 parts of water. are entered at room temperature, the bath raised to 80 within 1 hour and maintained at this level for another hour, at which time the dyeing process is completed. on removal the goods are rinsed and dried. To improve the dispersion, the dyestuif can be ground prior to dyeing with suitable wetting, dispersing and emulsifying agents, and preferably in the presence of inorganic salts,

e.g. Glauber salt. It can also be intimately mixed in aqueous paste form with a dispersing agent and then converted into powder form by drying at an appropriate temperature.

The present application is a continuation-in-part of ap- I plication Serial No. 489,771, filed February 21, 1955 (now US. Patent No. 2,866,678, patented December, 30, 1958).

Having thus disclosed the invention, what is c1aimed 1. The 1-amino-2-nitrobenzene-4-sulfonic acid amide of the formula parts of acetate rayon of the formula 2. The l-amino-Z-nitrobenzene-4-su1fonic acid amide of the formula 7. The i-amino-2-nitrohenzene-4-sulfonic acid amide of the formula 3. The 1-amino-2-nitrobenzene-4-su1fonic acid amide HO-CHg-CHz-O-CH: 15

HO-CHg-CH -O-CH: N0, N0: I 4. The 1-amino-2-nitrobenzene-4-sulfonic acid amide 2o H'CONHOSOPNH of the formula 8. The 1-amino-2-nitrobenzene-4-sulfonie acid amide of the formula NO: mc-o-cm 25 5. The 1-amino-2-nitrobenzene-4-sulfouic acid amide of the formula 30 -CHI SOP-NH CHr-CHg-O-CHg-CHg-O-CH:

References Cited in the file of this patent UNITED STATES PATENTS SOr-NH 2,866,678 Merian Dec. 30, 1958 H0 r- SOPNH 2,922,796 Adams et a1. Jan. 26, 1960 6. The 1-aimino-2-nitrobenzene-4-sulfonic acid amide FOREIGN PATENTS a 782,759 Great Britain Sept. 11, 1957 CHr-O-CHr-CHz-O-CH, 

1. THE 1-AMINO-2-NITROBENZENE-4-SULFONIC ACID AMIDE OF THE FORMULA 